Search

CN-116246942-B - Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and recording medium

CN116246942BCN 116246942 BCN116246942 BCN 116246942BCN-116246942-B

Abstract

The invention relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a recording medium. The present invention provides a technique capable of selectively forming a film on a desired surface with high accuracy. The method comprises (A) a step of forming an inhibitor layer on a first surface by supplying a modifying agent to a substrate having the first surface and a second surface, and (B) a step of forming a film on the second surface by supplying a film forming agent to the substrate after the inhibitor layer is formed on the first surface. Such that when the width of the inhibitor molecules constituting the inhibitor layer is WI, the interval between adsorption sites on the first surface is DA, and the width of the molecules X constituting the specific substance contained in the film former is WP, WP > DA-WI is satisfied when WI is smaller than DA, and WP > DAx-WI is satisfied when WI is larger than DA (X is the smallest integer satisfying WI < DAx).

Inventors

  • NAKAYA KIMIHIKO
  • YAMAMOTO RYUJI

Assignees

  • 株式会社国际电气

Dates

Publication Date
20260508
Application Date
20221129
Priority Date
20211208

Claims (17)

  1. 1. A substrate processing method, comprising: (A) A step of forming an inhibitor layer on a first surface by supplying a modifying agent to a substrate having the first surface and a second surface, and (B) A step of forming a film on the second surface by supplying a film forming agent to the substrate after the inhibitor layer is formed on the first surface, Such that, when the width of the inhibitor molecules constituting the inhibitor layer is denoted by WI, the interval between adsorption sites on the first surface is denoted by DA, and the width of the molecules X constituting the specific substance contained in the film-forming agent is denoted by WP, WI is less than DA satisfying WP > DA-WI, Wherein, x is the smallest integer satisfying WI < DAx, and the specific substance is at least any one of the raw material and the reactant, The substrate processing method further includes (C) a step of adjusting DA by at least one of heat treatment, etching treatment, reduction treatment, oxidation treatment, plasma treatment, and exposure of oxygen-and hydrogen-containing substances to the substrate, before the step (A).
  2. 2. The substrate processing method according to claim 1, wherein the kind of the modifier is selected in such a manner as to satisfy DA > WI and WP > DA-WI or in such a manner as to satisfy DA < WI and WP > DAx-WI.
  3. 3. The substrate processing method according to claim 1, wherein the kind of the specific substance is selected in such a manner that DA > WI and WP > DA-WI are satisfied or in such a manner that DA < WI and WP > DAx-WI are satisfied.
  4. 4. The substrate processing method according to claim 1, wherein in (C), DA is adjusted in such a manner as to satisfy DA > WI and WP > DA-WI or in such a manner as to satisfy DA < WI and WP > DAx-WI.
  5. 5. The substrate processing method according to any one of claims 1 to 4, wherein the adsorption sites of the first surface contain OH groups.
  6. 6. The substrate processing method of any of claims 1-4, wherein the first surface comprises at least any of an oxygen-containing film and a metal-containing film and the second surface comprises at least any of a non-oxygen-containing film and a non-metal-containing film.
  7. 7. The substrate processing method according to any one of claims 1 to 4, wherein the inhibitor molecule comprises at least any one of a hydrocarbon group, a fluorocarbon group, and a fluorinated silyl group.
  8. 8. The substrate processing method according to any one of claims 1 to 4, wherein the film-forming agent comprises a raw material and a reactant, and the specific substance comprises at least any one of the raw material and the reactant.
  9. 9. The substrate processing method according to claim 8, wherein (B) is performed a predetermined number of times by a cycle including (B1) a step of supplying the raw material to the substrate and (B2) a step of supplying the reactant to the substrate.
  10. 10. The substrate processing method according to any one of claims 1 to 4, wherein the film-forming agent comprises the raw material, the reactant, and a catalyst, and the specific substance comprises at least any one of the raw material and the reactant.
  11. 11. The substrate processing method according to claim 10, wherein (B) is performed a predetermined number of times by a cycle including (B1) a step of supplying the raw material to the substrate and (B2) a step of supplying the reactant to the substrate, and the catalyst is supplied to the substrate in at least one of (B1) and (B2).
  12. 12. The method according to any one of claims 1 to 4, further comprising a step of removing a natural oxide film formed on a surface of the substrate before the step (C).
  13. 13. The method according to any one of claims 1 to 4, further comprising a step of heat-treating the substrate after the step (B).
  14. 14. The substrate processing method according to any one of claims 1 to 4, further comprising a step of removing and invalidating at least a part of the inhibitor layer after the step (B).
  15. 15. A method for manufacturing a semiconductor device, comprising: (A) A step of forming an inhibitor layer on a first surface by supplying a modifying agent to a substrate having the first surface and a second surface, and (B) A step of forming a film on the second surface by supplying a film forming agent to the substrate after the inhibitor layer is formed on the first surface, Such that, when the width of the inhibitor molecules constituting the inhibitor layer is denoted by WI, the interval between adsorption sites on the first surface is denoted by DA, and the width of the molecules X constituting the specific substance contained in the film-forming agent is denoted by WP, WI is less than DA satisfying WP > DA-WI, Wherein, x is the smallest integer satisfying WI < DAx, and the specific substance is at least any one of the raw material and the reactant, The method further comprises (C) a step of adjusting DA by at least one of heat treatment, etching treatment, reduction treatment, oxidation treatment, plasma treatment, and exposure of an oxygen-and hydrogen-containing substance to the substrate, before the step (A).
  16. 16. A substrate processing apparatus includes: a modifier supply system for supplying a modifier to the substrate; A film forming agent supply system for supplying a film forming agent to the substrate, and A control unit configured to control an operation of a substrate processing apparatus to perform (A) a process of forming an inhibitor layer on a first surface by supplying the modifier to a substrate having the first surface and a second surface, and (B) a process of forming a film on the second surface by supplying the film forming agent to the substrate after forming the inhibitor layer on the first surface, wherein X is a minimum integer satisfying WI < DAx, and when a width of an inhibitor molecule constituting the inhibitor layer is WI, an interval of adsorption sites of the first surface is DA, and a width of a molecule X constituting a specific substance contained in the film forming agent is WP, WP > DAx-WI is satisfied when WI is smaller than DA, WP > DAx-WI is satisfied when WI is larger than DA, The control unit further performs (C) a process of adjusting DA by at least one of a heat treatment, an etching process, a reduction process, an oxidation process, a plasma process, and an exposure of an oxygen-and hydrogen-containing substance to the substrate, before (A).
  17. 17. A computer-readable recording medium having recorded thereon a program for causing a substrate processing apparatus to execute the steps of: (A) A step of forming an inhibitor layer on a first surface by supplying a modifying agent to a substrate having the first surface and a second surface; (B) A step of forming a film on the second surface by supplying a film forming agent to the substrate after the inhibitor layer is formed on the first surface; A step of setting WI as the width of inhibitor molecules constituting the inhibitor layer, DA as the interval between adsorption sites of the first surface, and WP as the width of molecules X constituting a specific substance contained in the film-forming agent, wherein X is the smallest integer satisfying WI < DAx, and wherein the specific substance is at least one of a raw material and a reactant, and Before (a), a step of (C) adjusting DA by at least one of a heat treatment, an etching treatment, a reduction treatment, an oxidation treatment, a plasma treatment, and an exposure of an oxygen-and hydrogen-containing substance to the substrate is performed.

Description

Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and recording medium Technical Field The present disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a recording medium. Background As a step of manufacturing a semiconductor device, a process of selectively growing and forming a film on a specific surface among a plurality of surfaces of different materials exposed on the surface of a substrate (hereinafter, this process is also referred to as selective growth or selective film formation) is sometimes performed (for example, see patent documents 1 and 2). Prior art literature Patent literature Patent document 1 Japanese patent laid-open No. 2020-155452 Patent document 2 Japanese patent laid-open No. 2020-155607 Disclosure of Invention Problems to be solved by the invention However, depending on the modifier and the film forming agent used in the selective growth, it may be difficult to selectively grow a film on a specific surface among a plurality of surfaces. It is an object of the present disclosure to provide a technique capable of selectively forming a film on a desired surface with high accuracy. Means for solving the problems According to one aspect of the present disclosure, there is provided a technique having: (A) A step of forming an inhibitor layer on the first surface by supplying a modifying agent to a substrate having the first surface and a second surface, and (B) A step of forming a film on the second surface by supplying a film forming agent to the substrate after the formation of the inhibitor layer on the first surface, Such that, when the width of the inhibitor molecules constituting the inhibitor layer is WI, the interval between adsorption sites on the first surface is DA, and the width of the molecules X constituting the specific substance contained in the film-forming agent is WP, WI is less than DA satisfying WP > DA-WI, WI > DAx-WI is satisfied when WI is greater than DA (x is the smallest integer satisfying WI < DAx). Effects of the invention According to the present disclosure, a film can be selectively formed on a desired surface with high accuracy. Drawings Fig. 1 is a schematic configuration view of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a view showing a portion of a processing furnace 202 in a longitudinal sectional view. Fig. 2 is a schematic configuration view of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and a portion of the processing furnace 202 is shown in a sectional view taken along line A-A in fig. 1. Fig. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a diagram showing a control system of the controller 121 in a block diagram. Fig. 4 is a diagram showing a processing sequence in one embodiment of the present disclosure. Fig. 5 (a) is a schematic cross-sectional view showing a surface portion of a wafer having a first surface and a second surface and a natural oxide film formed on the second surface. Fig. 5 (b) is a schematic sectional view showing a surface portion of the wafer after the natural oxide film is removed from the second surface by performing the cleaning step from the state of fig. 5 (a). Fig. 5 (c) is a schematic sectional view showing a surface portion of the wafer after the formation of the inhibitor layer on the first surface by the modification step from the state of fig. 5 (b). Fig. 5 (d) is a schematic sectional view showing a surface portion of the wafer after the film formation step is performed from the state of fig. 5 (c) to selectively form a film on the second surface. Fig. 5 (e) is a schematic sectional view showing a surface portion of the wafer after the inhibitor layer on the first surface is removed by performing a heat treatment step from the state of fig. 5 (d). Fig. 6 (a) of fig. 6 is a schematic cross-sectional view showing adsorption sites on the first surface of the wafer before the modifier is supplied. Fig. 6 (b) is a schematic sectional view showing a state in which inhibitor molecules are adsorbed at adsorption sites on the first surface of the wafer. Fig. 6 (c) is a schematic cross-sectional view showing a case where the inhibitor molecule forms steric hindrance to the molecule X constituting the specific substance contained in the film forming agent, blocking the molecule X from reaching the first surface of the wafer through the intermolecular gap of the inhibitor molecule. Fig. 7 is a schematic cross-sectional view illustrating a state satisfying WP > DA-WI when WI is smaller than DA, in which WI is the width of inhibitor molecule, DA is the interval between adsorption sites on the first surface of the